Method for protecting plants against infestation by mites and insects employing carbonate esters of 2, 4-dinitro-6-branched alkyl-phenols and sulphur analogs thereof



United States Patent METHOD FOR PROTECTING PLANTS AGAINST INFESTATION BY MITES AND INSECTS EM- PLOYING CARBONATE ESTERS OF 2,4-DINlTRO- 6-BRANCHED ALKYL-PHENOLS AND SULPHUR ANALOGS THEREOF Max Pianka and Donald John Polton, St. Albans, England, assignors to The Murphy Chemical Company Limited, Wheathampstead, St. Albans, England, a British company g p No Drawing. Filed Dec. 2, 1963, Ser. No. 327,527

19 Claims. (Cl. 167,'30)

This application is a division of application Serial No. 180,013, filed March 15, 1962.

This invention is concerned with improvements in or relating to pesticides. w

We have found that a novel group of organic carbonate esters have marked pesticidal activity, individual esters of the group possessing pesticidal activity in one or more of the following capacities: acaricidal, ovicidal, fungicidal, and insecticidal. Whilst some of the esters appear to possess significant activity against one particular pest, others possess activity against two or more pests. For example, some of the esters have marked acaricidal and ovicidal activity, whilst others are active against two different fungi. It will be appreciated that this dual activity is highly important in agriculture and horticulture.

Since the compounds according to the invention are not organophosphorus compounds they provide an alternative source of pesticides thereto, particularly for use in the control of mites resistant to organophosphorus compounds.

The present invention, therefore, provides as new compounds, compounds of the general formula:

in which X and Y are the same or different and each is an oxygen or a sulphur atom;

R is a saturated or unsaturated aliphatic hydrocarbon residue which may be substituted with one or more of the following substituents:

halogen atoms, amino groups, substituted amino groups, salted amino groups, hydroxyl groups, aryl groups, acyl groups, alkoxy groups, alkylthio groups, .alicyclic and heterocyclic groups; ,or is a phenyl, chlorophenyl, nitro'phenyl, naphthyl, tolyl, heterocyclic or alicypclic group; one of the groups R and R" is a nitro group and the other is an aliphatic hydrocarbon group having at least three carbon atoms, a phenyl, substituted phenyl, cyclohexyl or substituted cyclohexyl group.

R may, for example, bean alkyl group containing 1-18 carbon atoms, preferably 1-12 carbon atoms, e.g. methyl, ethyl, propyl, isopropyl, butyl, decyl etc.

R may, however, be an unsaturated aliphatic group e.g. anallyl or substituted allyl group.

As stated above X and Y may be the same or dilferent (lLCXSYR NO 1 (II) where R, X and Y have the meanings defined above and R is a branched alkyl group containing 3-8, preferably 4-8, carbon atoms.

Particularly useful compounds of formula II are those in which R represents a sec-butyl group a tertiary butyl group [(CH -C-], a l-methylbutyl group [C H -CH-(CH or a l-methylheptyl group 6 13' 3) Many compounds of general Formula II possess good acaricidal activity and some also possess fungicidal activity against powdery mildews, for example cucumber powdery mildew (Erysiphe cichoracearum) and apple mildew (Podosphaera leucotricha). Some of the compounds of general Formula II also possess ovicidal activity against eggs of mites.

Other compounds of general Formula II, e.g. isopropyl 2,4-dinitro-6'-sec.-butylphenyl carbonate also possess activity against the diamond backed caterpillar (Plutella maculipennis) Those compounds of Formula II in which R is a straight or branched chain alkyl group containing from 1 to 8 carbon atoms or is a tetrahydro-furfuryl group, were found to be especially useful, many of them having good multi-pesticidal activity.

Particularly preferred individual compounds according to the invention on account of their outstanding pesticidal activity are the following:

(a) Isopropyl 2,4-dinitro-6-'sec.-butylpheny1 carbonate CH: C 2115- C H- 0.001%. It also shows good activity .against cucumber powdery mildew, apple mildew and diamond backed caterpillar. This wide range of pesticidal activity makes the compound very important for many horticultural pur-' poses.

('b) 1-methy1hepty1 2,4-di1iitro-6-sec.-butylpheny1 carbonate This compound shows very good acaricidal. activity.

(c) 1'-methylbuty1 2,-dinitro-6-sec.-butylpheny1- carbonate I NO:

This compound has very good acaricidal activity and has given 100% kills at concentrationsof 0.005%. It is also. very active against apple mildew and cucumber. powderymildew.

(d) 3'- (and 2'-) methylbutyl 2,4.-dinitro-6-sec.-buty1- phenyl carbonate 1 102 and CH3 $130.0 CHgHLCzH These compounds are outstandingly active against. greenhouse red spider andshave given kills of 98% at They also show good.

concentration of only 0.001% activity against apple mildew.

(e) a-Tetrahydro-furfuryl 2,4-dinitro-6-see.-buty1pheny1 carbonate 0.00.0-CHrL J 1 CzH (lJH N02 7 CH3 This compound is also very active. against greenhouse red spider and has given 100% kills at concentrations; as

low as:0.0005%. It alsoshows very good activity against both cucumber powdery mildew and apple mildew.

(f) Verysimilar properties are shown by methyl 2,4-dinitro 6-sec.-buty1phenyl thiolocarbonate (I). C O .S C H:

(g) Methyl 2,4-dinitro-6-terta-butylphenyl carbonate This compound has good activity; against greenhouse red spider combined witliimarked 'ovicidal activity.

(h) Ethyl "2g4fdinitro-fi-tert.-buty1pheny1carbonate (i) n-Hexyl 2,4-dlnitro-6-tert.-butylpheny1 carbonate,

0.00.0.CaHu CH3" I 011330 No; on,

This compoundis distinguished by-good'acaricidal ac-, tivity. 1

This compound has goodlactivity'against greenhouse. red 3 spider as:-well Eas good activity both against cucumber; powdery mildew and apple. mildew..

(k) Isobr opyL ZA-dlnitro-B- (1'.-methy1 butyl) ,-phei1y1 carbonate. V

on: i

This'compound has gqo d'a ctivity against greenhouse red i. spider and also :possesses ovicidat,activityas wellr as marked activity; againstspowdery mildew.

(1) 3'- (and 2-)m'ethylbutyl 2,4-dinitro-6-(i -methylbutynphenyl carbonate CH3 C3H7-?H-* N02 0 NO: and 10 O.CO.OCH2CHCH.CH:

CH3 C3H7'CH NO3 1 lo CH3 These Compounds combine very good activity against greenhouse red spider with good activity against apple mildew.

(m) Ethyl 2,4-(linitr0-6-(l-methy1heptyl)-phenyl carbonate O.CO.O.O2H

otns-on- N0, 7

(n) Methyl 2,4dinitro-6-(1-1nethylheptyl)-pl1enyl carbonate 3-5 (l).C0.0.CHa otrr,3-'cn- 1 NO;;

(0) Methyl 2,4-dinltro-6-(l-methylheptyl)-phenyl thionothiolo-carbonate This compound showed good activity against greenhouse red spider and cucumber powdery mildew.

(p) Methyl 2,4-di1itr0-6-(1-methylheptyl)-phenyl This compound showedgood activity against apple mildew and apple scab and also showed excellent eradicant 8 properties towards these fungi. This dual activity is, of course, extremely important in practical application.-

Compounds of the formulae were found to possess excellent activity against spider mites resistant to organophosphorus compounds such as parathion (0,0-diethyl -O-p-nitrophenyl phosphorothioate) and schradan (octamethylpyrophosphoramide). Moreover many compounds of these general formulae also exhibit aphicidal activity and activity against caterpillar.

The compounds according to the invention may be prepared in any desired way. In one convenient method of preparation of compounds of general Formula I, the corresponding phenol:

R (IV) where R and R" have the meanings defined above, may

be reacted with a haloformic acid ester of the formula:

Z.CX.YR (V) where X, Y and R have the meanings defined above, and

R (VI) (where R and R" have the meanings defined above and 1M represents an alkali metal, preferably sodium or potas- -sium) with a haloformic ester of the formula:

Z.CX.YR v

(Where X, Y, R and Z have the meanings defined above) in solution in an inert organic solvent. Particularly suitable solvents for this reaction are ketones, e.g.- acetone.

The phenoxide of Formula Vi may be preformed or,

preferably, may "beformed in situ in the inert organic,

solvent prior to introduction of the haloformic acid .ester by reaction of the parent phenol with a suitable alkali metal compound, e.g., thehydroxide, carbonate or ;bicarbonate. 7

The preparation of the compounds according to the invention by the .reaction of a phenoxide of general For-.

mula VI with a compound of general Formula Vis particularly advantageous since the use of the phenoxide in place of the parent phenol (IV) and a tertiary base leads,

in general, to improve yields being obtained.

However, another advantageous method of preparing I the compounds according to the invention comprises. the

simultaneous reaction of the parent phenol (IV) with a haloformic acid ester (V) in an inert organic solvent (e.g., a :ketone such as acetone) in the presence of an alkali metal carbonate or alkali metal bicarbonate, pref-;

erably an alkali metal carbonate. By using this method,

it is also possible to obtain improved yields as compared with the, use of the parent phenol (IV) and a tertiary base. It is, to be observed that alkali metal hydroxides cannot be usedin place of alakli metal carbonate or al-, kali metal bicarbonate since these will decompose the.

haloformic acid ester.

The haloformic acid esters (V) may conveniently be prepared by reaction of a compound of the formula RYH with a compound of the formula CXZ according to the.

Thus, the preferred chloroformic acid esters maybe produced by the following reactions:

In general, these reactions may be carried out in the.

presence of aluminum chloride as catalyst and where re-,

quired in the presence of an .acid binding agent.

The new compounds according to the invention can be formulated for use in any desired way. Generallysuch formulations will include the compound .in association with a suitable carrier or diluent.

.45 Such carriers may be liquid or solid and designed to aid the application of thew, I compound either by Way of dispersingit where it is-to be applied or to provide-a formulation which can be made by'the user into a dispersible preparation.

Liquid preparations thus include preparations of the a compound in the form of solutions or emulsions which can be used on their own or be adapted to be made .up

with water or other diluents to form sprays etc.; in such cases the carrier is a solvent or emulsion base non-phy-.

Generally such prep- 7 totoxic under the conditions of use. arations will include a wetting, dispersing or emulsifying agent.

liquid diluents such as clays,-which may themselves have wetting properties, and/or wetting, dispersing or emul-i Such preparations may include inert solid or Other liquid. preparations include" aerosols in a which thecompound is associated with a liquid carrier.

sifying agents; binding and/or adhesive agents may, also be included. Solid preparations also include thermalfumigating mixtures wherein the compound is associated a with a solid pyrotechnic component.

For the better understanding of the'inventiom'the foltionship of grams to ccs. Reference in the examples to resistant spiders. indicates that these. were substantially I resistantto attack by organophosphorus compounds such as, for example, parathion and schradant The tests against cucumber powdery mildew (Erysiph cichoracearum), apple mildew. (Podosplzaera leucotricha) and apple scab (Venturia inaeqztalis) were effected as follows:v

Test for activity againstErysiphecichoracearum.The wetta'ble powder wastdiluted with water to obtain the; required concentration of. the toxicant. Cucumber plants were sprayed with this dilution and placed in a'greenhouse under artificial illumination Spores of cucumber mildew were blown onto the plants. Another spraying was carriedtoutafter 10 days and the incidence of infection assessed-at the end of the treatment. Wherea dust isindicated in the tables, the cucumber. plants were dusted with'a dust prepared by mixing 5 parts of the toxicant with 595 parts of china clay instead of being sprayed with the .wettable powder. Otherwise the technique of infection and the .a-ssessment'of the incidence of the infection after treatment'were thesame.

Test for activity against Podo'sphaera leucotricha.'

The wettable powder was diluted with water tothe requiredvconcentration of the toxicant. Apple rootstocks placedin a greenhouse under artificial illumination were sprayedwith this dilution. Spores of apple mildew were.

stocks were sprayed=under artificial'illumination with this mixture;- After several hours the deposite had dried. On the same; day thGjI'OOt-StOCkSQWOIB placed in an infection chamber and they upper surfaces of the leaves were sprayed with a suspension containing approxl, 500,000

spores of Venturia inaequalisper cc, After 48 hoursthe rootstocks were removed :from the infection chamber and placed in a greenhouse under artificial illumination. The infection incidence was then assessed after 21:days.-

Example 1 .-Isopr0pyl, 2,4-dinitr0-6-sear buryl-phe'nyl carbonate The basic equations underlying .thepreparation of this compound are;

lowing examples are given by. way of illustration only. In these examplestemperatures are given in degrees centigrade,. and parts, unless otherwise. stated are by weight.

Where parts by weight and parts by volume are men-'- tionedtogether these are to be taken as having the relawas-dissolved with stirring-in acetone (4'00 cct).

9 and the mixture stirred till all reactants were in solution; To this solution was added, all at once, a solution of isopropyl chloroformate (96% pure, 25.3 g.) in acetone (100 cc.). The mixture was refluxed for 2 hours. After .cooling, the precipitated potassium chloride was filtered off, washed with a little acetone, dried and weighed. Weight ofpotassium chloride was 14.5 g. (98% of theoretical). The acetone was then stripped off. To the residue (71.2 g.) was added methanol (100 cc.) and the solution stirred. Crystallisation started immediately and continued overnight. The crystalline solid was filtered oif and washed on the filter with very little methanol to give almost colourless washings. The white crystal- "line solid (first crop) weighed 46.6 g. (71.5% of theoretical), M.P. 55-57". The mother liquor (without the washings) was kept overnight at 9". The second crop of a white crystalline solid was filter'ed off weighing 7.8 g. (12% of theoretical), M.P. 54-57". On recrystallisation from petrol, B.P. 40-60, almost white crystals, melting, at 56-57", were obtained. (Found: N, 8.46. C14'H13N2O7 requires N, Total yield of isopropyl 2,4-dinitro-6-sec.-butylphenyl carbonate was therefore 54.4 g. (83.5% of theoretical).

By repeating this method but using sodium carbonate or potassium carbonate instead of potassium hydroxide,

fisopropyl.2,4wdinitroesec.ebutylphenyl carbonate was ob- .tained in 81% yield and 91%. yield respectively.

This compound has exceptionally good acaricidal activity coupled with safety to living plants, and has a very favourable mammalian toxicity: acute oral LD50 to male mice is greater than 1500 mg./kg., acute oral LD50 to male rats is about 400 mg./kg. body weight.

The compound was formulated as follows: parts of the compound were mixed with 20 parts of Lissapol NX (a polyethylene glycol ether) and made up to 100 parts by volume with acetone. This solution was diluted with water to contain 0.001% of the compound. Dwarf bean plants were infested with 50 resistant greenhouse red spiders per plant. The plants were dipped in the diluted solution and observations were made after 48 hours, when it was found that all the spiders were dead. In parallel tests schradan (octamethylpyrophosphoramide) and parathion (0,0-diethyl O-p-nitro'phenyl phosphorothioate) at concentrations of 0.05% of toxicant gave only 20% and 30% kills of this resistant spider respectively.

The compound was also formulated as a 50% wettable powder as follows: a mixture of 50 parts of the toxicant, 7 parts of finely divided synthetic calcium silicate, 6 parts of powdered calcium salt of sulphite cellulose waste liquor, 0.5 part of 80% sodium lauryl sulphate and 38.5 parts of china clay having a state of subdivision such that at least 95% thereof passes through a 300 mesh B.S.S. sieve, was intimately mixed and ground. When required for use the powder was mixed withwater to give the desired concentration. When diluted to 0.001% of the toxicant and sprayed on bean plants infested with resistant greenhouse red spider it gave a complete kill of spider after 48 hours.

The compound was also effective against Plutella maculipennis giving a complete kill of the second and third instar at a concentration of 0.05% of toxicant.

The compound gave complete protection against cucumber powdery mildew '(Erysiphe cic'h'oracearitm) at a concentration of 0.05% of the toxicant and against apple mildew (Podosphaera leucotricha), with no phytotoxicity to the foliage or fruit.

A conventional thermal fumigating device was prepared containing 30% by weight of the toxicant in admixture with potassium chlorate, lactose and china clay. The quantity of toxicant was calculated so that, on ignition, it yielded 1 g. of toxicant in 1000 cubic feet of space. house red spider were placed in a cubicle and the device Cucumber plants infested with resistant green-' 10 ignited. Observations after 48 hours were 'made when it was found that all thespider was killed.

An aerosol was prepared in which the toxicant was dissolved in acetone to give a 10% w./v. solution. This was dispersed with the aid of compressed air to yield 1 g. of toxicant per 1000 cubic feet. This was applied to cucumber plants infested with resistant greenhouse red spiders. After 48 hours it was found that all the spiders were killed. No phytotoxicity to the plants were observed from these treatments.

The product was also formulated as an emulsifiable concentrate as follows: 3 lbs. of the toxicant were mixed with 0.75 lb. of a blend of an aryl alkyl sulphonate, an alkyl aryl polyethylene oxide ether and an alkyl polyethylene oxide ether and made up to 1 gallon with coal tar naphtha, of which boils below 190. This gave similar acaricidal and fungicidal results it those given by the wettable powder.

- Example 2.-1-methyllzeptyl-2,4-dinitr0-6-sec.-buty'lphenyl-carbonate To a solution of 2,4-dinitro-6-sec.-butylphenol (60 g.) dissolved in ether (500 cc.) was added pyridine (20 g.) and then, while cooling and stirring, a solution of octan- 2-yl chloroformate (48 .g.) in ether cc.). Pyridine hydrochloride precipitated immediately and was filtered .Qt andt as' hs a s utiqnw s r th d lut h d ochloric acid, then with water. The ethereal solution was then dried over anhydrous sodium sulphate, filtered. and the ether removed leaving a clear brownish oil, weighing 98 g. (theory requires 99 g.). It had a refractlV index "D20 (Found N, C I-1 N 0 requires N, 7.07%.)

This oil was formulated as a 25% wettable powder as follows: 25 parts of the oil, 15 parts of a polyoxyethylene oleate, 20 parts of finely divided synthetic calcium silicate and 40 parts of finely divided china clay (as described in Example 1) were mixed and ground. When diluted to 0.01% and applied to resistant greenhouse red spider on dwarf beans it gave complete kill of the spider. Moreover this compound was effective against fruit tree red spider (Panonychus ulmi) giving a complete kill of spider adults when fruit trees in orchards were sprayed with this wettable powder at a concentration of 0.025% of the toxicant. It caused no damage to foliage or fruit.

Using the general method of Example 2, further com pounds of the general formula VII below were prepared by reaction of the corresponding phenol with the appropriate chloroformic acid ester.

C C H- N02 (VII) For the sake of convenience the nature of the products, their characteristics and yields obtained, together with biological results are shown in Table I.

The abbreviation W.P. indicates wettable powder which, in the case of the 12.5% W.P. was prepared as follows: 12.5 parts of the compound, 0.25 part of 80% sodium lauryl sulphate, 6 parts of powdered calcium salt of sulphite cellulose waste liquor, and 81.25 parts of fine china clay (described in Example 1) were intimately mixed and ground. The other W.P.s were prepared in like manner.

In order to prepare a 5% miscible preparation 5 pants of the compound were mixed with 10 parts of Lissapol NX and made up to 100 parts by volume with acetone or another suitable solvent. Other miscible preparations are made using a similar procedure.

TABLE I Resistant Erysiphe Potiosphaem Greenhouse cichoracearu'm leucotrz'cha Red Spider Example Yield No. X Y R M.P. C a per- Formulation cent Conc Kill Conc. Protec- Cone Protec- (per- (perer-. tion (pertion cent) cent) cent). (percent) "(percent) cent) 90 12.5%W.P 0.001. 98 0.05 100 91.5 5% miscible.-. 0.001 99 91.5 .do' 97' mmwooooooooooo 000000000 owmmoooooooooo 0 000000000 miscible. CHzCHzCl 77-79 86 ..-.-d CH2CH2OC2H5--- 87 (1O.. CHz-CHZOHz 91 misoible-; CHzCHBf-OHyBl- 79 5% miscible. CHgCaHs ..d0 CaH 44 10% miscible-. p-Ohlorophenyl- 50 Y 5% miscible. Cyclohexyl 77 .do V a-Naphthyl 1. 6030 99 10% miscible-. V

09H; W 42-44. 5 98 l 5% miscible... CH: 1 -86 (l CQFTK 1. 5954 09H; 1. 5571 1 From dl-isopropyl ether. 18 From methanol From petrol, B. P. 30-40. Low melting solid.

Usingthe general methodbf Example 1 further comn pounds of the general Formula V11 above were preparedby reaction of potassium phenoxide of the formula with the appropriate chloroformic acid ester.

iWhCIl the final product was found to be contaminated with unreacted 2,4-dinitro-6-sec.-butylphenol, the product was dissolved in benzene and stirred for several hours with excess powdered potassium hydroxide or anhydrous potassium carbonate. The benzene solution was then filtered from the solid consisting of excess of potassium hydroxide or potassium carbonate and potassium 2,4-

dinitro-6-sec.-butylphenoxide and the benzene removed.

from the filtrate under reducedpressure.

Example t29.-p-Nitrophenyl 2,4,-dinitr0-6-sec.-:

butylphenyl carbonate This compound: was prepared from p-nitrophenyli chloroformate and .2,4-dinitro-6-sec. butylphenol accord-; ingv =to the'rnethod described .inExample 2, butusingq.

Example 30.-2-mercaptobenzthiazolyl 2,4,-dinitr0-6-sec.- 1

but-ylphenyl 'carbonate' i This compound .was; prepared from: Z-inercaptobenzthiazolyl chloroforrnate and 2,4-dinitro-6-secwbutylphenol 3 using the method described in EXample 29. 4 The desired compound was obtained as a solidmelting at 163- 165 after; recrystallisation from ethyl acetate. (N as nitro groups, Found N, 6.3;.required N, 6.5%.) It was formu- TABLE II Resistant Erysiphe Padosphaera Greenhouse cichomcearum leucotricha- Red Spider Y R M.P. 0. Yield Formulation j Example No X (percent) a Cone Kill: Conc. Protec Cone. Promo- (per- (per- (pertionu (pertion cent) cent) cent) (percent) (per-.

cent) cent) 2 O O -Tetrah droiuriur 1 39-41 93 12.57 WLP--- 0.0005 0.05 99: 0.05 100 2g O S 3113-03 -Z 62-65 78 25% all 0.0005 100 0.05 99 0.05 100;

1 From petrol B.P. 4060.

13 lated as a 12.5% wettable powder and it gave 87% kill of resistan't'greenhouse red spider at a concentration of 0.01% of the toxicant.

Example 31. N,N-diethylaminoethyl 2,4-dinitr-6-tertbutylphenyl carbonate To a solution of phosgene in ether w./v.; 20 cc.) was added a solution of diethylaminoethanol (3.9 g.) in ether (10 cc.), while stirring, at about 0 C. The solid that precipitated was washed with e ther by decantation and to a suspension of this solid in ether was added a solution of potassium 2,4-dinitro6-tert.-butylphenoxide (9.3 g.) in acetone (50 cc.). Stirring was continued for two hours and the mixture filtered from the solid. The filtrate was evaporated to dryness, and the residue recrystallised from isopropanol. It Was then dissolved in methanol, neutralised to pH 7 with N/2 alcoholic potassium hydroxide. Methanol was then evaporated ofi and the residue extracted with benzene. The benzene solution was filtered ofi from the soluble solid, the benzene 2,4-dinitro-6-sec.-butyl phenoxide and fi-ethylthioethyl chloroformate in acetone. The precipitated potassium chloride was filtered off, acetone was removed from the filtrate, and the residue extracted with benzene. After filtration the benzene was removed from the filtrate leaving a yellow brown oil (42% of theory), n 1.5441.

Using the general method of Example 1 the following compounds of the general Formula VIII O.CX.YR CH3\ CH3C-- NO2 N02 (VIII) were prepared from 2,4-dinitro-6-tert.-butylphenol, potassium hydroxide and the appropriate chloroforrnate. Where necessary the reaction mixtures were refluxed until the reaction was complete and no more potassium chloride precipitated.

TABLE III Resistant Eryst'phe Podosphaera 1 Greenhouse cichoracearum Zeucotricha Example Yield Bed Spider No. X Y R M.P. 0. percent Formulation Cone.v Kill Cone. Protec- Cone. Protec- (per- (per- (pertion (pertion cent) cent) cent) (percent) (percent) cent) 0 0 CH 98.5-99.5 67 W.P. 0.005 98 O 0 C2 5.. 66.5-67.5 75 25% W.P. 0.005 100 O O n-C4H 49 51 79 5% miscible... 0.0005 97 O O ggg gggggf ggfgfg 60-61 91 25% WP 0.0005 100 0. 05 100 0. 05 100 o 0 oH,oH=orn II 52-55 50 5% miscible 0. 005 100 1 From petrol (B.P. 40-60"). 1 From petrol (B.P. (ED-80). 3 From methanol.

4 From aqueous methanol.

remaining residue recrystallised from di-isopropyl ether. 121 were obtained.

This material showed the following acaricidal activity:

Using the general method of Example 32 the following compounds of the general Formula VIII were prepared from potassium 2,4-dinitro-6-tert.-butyl phenoxide and the appropriate chloroformate.

TABLE IV Resistant Greenhouse Example X Y R M.P. C. Yield, Formulation Red Spider N0. percent Cone. Kill perpercent .cent

0 O H-CQHM- 1 -51 62 5% miscible... 0.001 98 O O D-C10Hz1 44-46 82. 5 -,d0; U. 01 98 O O CHQCHgCl 1b 74. 5-76 82. 5 100 O O CHzCHzOH 14 162-165 35 62 0 0 011261120 Cal-I5 59-60 70 98 O O CI-IzCHgOCOCgHn- 101-102. 5 65 100 0 0 GHQ-O 10 82-83 100 O O -CH .C H4CI 90-91 69 82 O O p-Tolyl 89-91 33 98 O O a-Naphthyl- 154-155 25 87 From petrol (B.P. 3040).

From methanol.

1d From methyl ethyl ketone. 10 From petrol (B.P. Ell-160). 1b From petrol (B.P. 80). From petrol (13.1 IO-60). From didsopropyl ether.

at .01% of toxicant it gave kill of the resistant greenhouse red spider.

Example 32.fl-ethylthi0ethyl 2,4-dinitro-6-sec.-

' butylphenyl "carbonate This compound was prepared by reacting potassium chloroformate, but using benzene as the solvent of reaction.

TABLE V Resistant Green- .Podosphaera 7 house Red Spider lerlcotricha Example No. X Y R M.P. C. m," Yield Formulation percent C0110. Kill Cone. Proteo- (percent) (percent) (percent) tion (percent) 0 O n-C1H 40. -41. 5 95 25% W21 0. 001 O 0 n-CH 1-. 100 5% miscible 1 0. 01 O O CG(CHa'): 1 120-122 0.005 O O CH(CH3)CH5.. 0.01 O O CH(GH )C H 0. 01 O O CHqCILBrCH BL 0. 01 O O wTetrahydro-iuriuryL- 0. 01 O O Cyclohexyl 0. 01 O S CH3- 0. 01

S S CH 0.01

1 From di-isopropyl ether.

18 From petrol, B.P. 4060. From methanol. Low melting solid.

Using the general method of Example 2 the following 2,4-dinitro-6-sec.amylphenyl carbonate), gave also 95% compounds of the general Formula 1X kill of the spores of Venturia inaequalis'(apple scab): at;

a concentration of toxicant of 0.006%. O C X YR Using the general method of Example 2 the following compounds of the general Formula X C3H7.CH N02 7 H3 00.1mm

CuHnCH NO: NO; (IX), v 7 Hz were obtained from 2,4-dinitro-6-see:amylphenol and the V appropriate chloroformate. (X)

TABLE VI Resistant Erysiphe Podosphaera Greenhouse cichoraceamm lcucotricha Red Spider Example 1 Yield,

No. X Y R M.P. C. a percent Formulation Cone. Kill Cone; Protec- Cone. Protec- (per- (per- (per--, tion (pertion cent) oent) cent) (percent) (percent) 7 cent) 0 o 79 25% W.P 0.001 p 100 0. 05 99 0 0 s9 25% W.P 0.001 100 0.05 99 0.05 100 0 0 92 5% miscible--- 0.01 V94 0 0 88 do o.01 2 88 0 0 100 -e d0; 93 0 0 98v 25%W.I 100 0.05 100 0 0 100 5% miscible-.- 0.001 100 0 0 d 91 0 0 66 I 84 -7 o 0 s1 25%W.P 0.005 g 100 -l 0.05 100 o 0 67 5% miscible- 0.005 f 100 0 Q 81' 20% W.P 0.001 100 005 100 0 0 83 5% miscible- 0.001, 100 0 0 69 do 0.01 95 0 0 91 0.01 93 0 0 ml 98 0.01 93 O O p-Chlorophenyl 16 0. 01 O 0 a-NaphthyL- 87 p 0. 01 99 O O Cyclohexyl- 100 0. 01 98 0 s cm 87 0.01 96 1 From methanol. From di-isopropyl ether. From petrol, B1. 3040" Products of Example 58 (methyl 2,4-dinitro-6-sec: were obtained from 2-?(1 methyl-n-heptyly-'4,6 dinitroe amylphenyl carbonate) and of Example (a-naphthyl, r7 phenol and the appropriate chlorofo'rmate.

TABLE VII Resistant Erz/siphe Podosphaera Sphaerotheca Greenhouse cichoracearam leucotricha pannoaa Red Spider Example Yield,

No. X Y R 12 5 percent Formulation Conc. Kill Pro Cone. Cone Pro- Cone. Pro- (per- (pertection teetion (pertection (pertcction cent) cent) (per- (percent) (percent) (porcent) cent) I cent) cent) CH 1.522 100 20% W.P 0.01 77 0.0125 100 0. 0063 100 O 03H5 1.513 92.5 12.5% W P 0.01 8?, 0.0125 100 0.0003 100 i 0 CH(CH3) 1.505 V 100 0 CHtCHQOfl-L 1.492 .P 100v 0.04 100. O CH(CH3)COH13 1. 502 98 O .a-TetrahydrofurfuryL 1. 514- 94 5% miscible... 0.001 76 S CH 1. 563 93.8 25% W.P 0.0125 g 100 0.0125 100 1 The compounds oithese examples also gave virtually 100% control of Venturia inaequalis when applied as a 12.5% W.P. at a concentration of 0.125%

of toxicantto rootstocks in ected with Ventaria maeqaalis.

Example 85 Methyl 2 ,4-dinitro-'6-(l-methylheptyl)- phenyl thiolocarbonate To a solution of 2,4-dinitro-6-sec.-octylphenol (6.6 g.; 90% pure) in acetone (40 cc.) potassium hydroxide (1.13 .g.) was added. This mixture was stirred at room temperature until a complete solution was obtained. To it a solution a methyl thiolo-chloroformate (2.2 g.) in acetone (10 cc.) was added all at once, the mixture heated under reflux for 30 minutes and allowed to stand for 16 hours at room temperature. The precipitated p0.- tassiurn chloride was filtered on (1.29 g.; 94.5% of theory) and the acetone removed from the filtrate under reduced pressure. A brown oil, r1 1.534, weghing 9.9 g., was obtained.

When applied to cucumber mildew (Erysiphe cichoracearum) as .a 12.5% W.P. (wettable powder) at a concentration of 0.00625 of toxicant it gave 98% protection. When applied as a 12.5% wettable .powder at a concentration of 0.025% of toxicant to rootstocks infected with Venturia inaequalis it gave 94% control.

This dual activity is most important in practice. In addition the product had excellent eradicant properties against these fungal infections.

Example 86.-Ethyl '2,4-dinitr0-6-cyclohexyphenyl carbonate To a solutionof 2,4-dinitro-6-cyclohexylphenol (5.65 g.) and pyridine (1.6 g.) in ether (200 cc.) ethyl chloroformate (2.15 g.) was added with stirring. The precipitated pyridine hydrochloride was filtered after 30 minutes and the ether evaporated off from the filtrate. The residue was recrystallised from petrol (B.P. 40-60") yielding pale yellow prisms, M.P. 76, of ethyl 2,4-dinitro-6- cyclohexylphenyl carbonate (3.9 ,g.). (Found: N, 8.1. C l-1 N O requires N, 8.3%.)

This was formulated as follows: 10 parts of the toxicant were mixed with 15 parts of Lissapol NX and made up to 100 parts by volume with acetone. 80% kill of resistant greenhouse red spider was obtained at a concentration of 0.01% of the toxicant.

A 5% dust containing 5 parts of the product and 95 parts of china clay applied to cucumbers gave 99% ,protection from Erysiphe cichoracearum.

Example 87 .M ethyl 2,4-dinitr0-6-phenylphenyl carbonate To a mixture of 2,4-dinitro-6-phenylphenol (5.2 g.), pyridine 1.63 cc.) and tetrahydrofuran (150 cc.) was added, with shaking, methyl chloroformate (1.89 g.). The mixture was set aside for 24 hours at room temperature, then filtered. Tetrahydrofuran was distilled off from the filtrate and the residue recrystallised from di-isopropyl ether to yield 3.6 g. of a solid, M.P. 123-4245". (Found: N, 8.8. C14H1QN207 requires N, 8.8%.)

It gave 90% kill of aphids at a concentration of 0.1% of the toxicant.

In addition this compound showed excellent fungicidal --activity against the spores of Venturia inaequalis, Botryfis cinerea, and Fusarium bulbigenum. The test used was that described by Montgomery and Moore, J. Pornol, 1938,15, 253.

Example .88.Ethyl 2,4-dinitro-phcrzylphenyl carbonate Example 89.-Methyl 2,4-.dinitr0-.6-phenylphenyl thiolothionocarbonate To a solution of 2,4-dinitro-6-phenylphenol (15.6 g.) and pyridine (4.9 co) in hot benzene (600 cc.) a solution of methyl thiolothionochloroformate (7.59 g.) in benzene (20 cc.) was added. The mixture was allowed to stand for 24 hours. Water was added to the reaction mixture, the benzene layer separated, dried over anhydrous sodium sulphate-filtered, the benzene removed under reduced pressure from the filtrate and the residue recrystallised from alcohol yielding a crystalline solid melting at 132-133 (Found: N, 7.7. 'C14H10N2O5S2 requires N, 8.0%.)

It gave a complete kill of resistant greenhouse red spider at a concentration of 0.01%

Example 90.Ethy'l 2,4-din'itr0-6-is0pr0pylphenyl carbonate This compound was prepared as described in Example 2 from 2,4-dinitro-6-isopropylphenol and ethyl chloroformate. The oil that was obtained crystallised on standing. On recrystallisation from petrol .(B.P. 3040) pale yellow prisms were obtained, M.P. 58.559 (60% yield). (Found: N, 9.1. C12H14N207 requires N, 9.4%.)

It gave a complete kill of resistant greenhouse red spider at a concentration of 0.01% of toxicant.

Example 9 1.'E'lhyl 2,6-dinitr0-4-tert.-butylphenyl carbonate This compound was prepared as described in Example 2 from 2,6-dinitro-4-tert.-butylphenol and ethyl chloroformate, using benzene instead of ether as solvent of reaction. On recrystallisation from alcohol a crystalline solid was obtained, M.P. 7879 (76% yield). (Found: N, 8.9. C H N O requires N, 8.9%.

It gave 80% kill of resistant greenhouse red spider at 0.005%.

Example 92.Is0pr0pyl 2,6-dinitro-4-lert.-butylphenyl carbonate This compound was prepared as in the case of Example 91, but using isopropyl chloroformate. A crystalline solid :Was obtained, M.P. 97 9s 39% yield).

Example 93.-Isopropylv 2,4-dinitr-6-sec.-butylphenyl z carbonate 2,4-dinitro-6-sec.-butylphenol (12.0 g), potassium car-.

bonate (3.53 g.) and isopropyl chloroformate were re-- flexed with stirring in acetone (50 cc.) for 3% hours. After this time the precipitated potassium chloride Was filtered off and the filtrate evaporated .to dryness in vacuo; The residue was dissolved in methanolqand allowed .to.

crystallise. The desired compound (M.P.' 55-58-),, was obtained in a yieldof 96% Thefollowing results were" obtained by dipping plants.

infested with resistant greenhouse red spider, inorder to demonstrate the. ovicidal action of the compounds:

1 Ovicidal action Compound of I Examp'loNo. Formulation Cone. of toxi- Kill oteggs, cant, percent percent 0.025 96 33 W.I 0.01 71 0. 005 63v 0.025 94 34 12.5% W.P 0.01 77 v O. 005 69 i 4 0.025 89 36 25% W.P 0. 01 84 0.005 67 0.025 87 48 25% W.P.J 0. 01 65 1 c 0.005 52 0. 025 94 58 25% W.P 0.01 87 O. 005 84 We claim:

A'method of protecting plants against infestation by mites and insects, comprising applying to saidplants an effective but non phytotoxio amount of isopropyl. 2,4-dinitro.-6-sec.-butylphenyl carbonate.

2. A method of protecting .plants against infestation by mites and insects, comprising applying to said plants'an effective but non-phytotoxic amount of 1'-methylheptyl 2,4-dinitro-6-sec.-butylphenyl carbonate.

3. A method of protecting plants against infestation by mites and insects, comprising applying to said plantsan effective but-non-phytotoxic amount of 1-rnethylbutyl 2,.

4-dinitro-6-sec.-butylphenyl carbonate.

4.-A method of protecting, plants against infestation by mitesand insects, comprising applying to said plants an effective but non-phytotoxic amount. of 2.-methylbutyl 2,

4-dinitro-6-sec.-butylphenyl carbonate.

5. A method of protecting plants against infestation by mites and insects, comprising applying to said plants an effective. but non-phytotoxic amount of;3-methy1butyl '2,4.-,

dinitro-6-seo-butylphenyl carbonate.

6. A method of protecting plants against infestation by mites and insects, comprising applying to said plants an mites andinsects;.comprisingtgapplying to said plants an .,eifective but HOIl-phytOtOXiC amountaof methyl .2,4-d1mtro- 6-sec.-butylphenyl thiolocarbonate'.

8; Amethod of protecting plants against infestation by mites and insects, comprising. applying to said plants an effective but non-phytotoxic amou'nt'of methyl 2,14-d1n1trot 6-tert.-;butylpheny1 carbonate} 7 9. A method of protecting. plants against infestation .by. mites and insects,- comprising. applying .tosaidplantsan 2 effective but'non-phytotoxic amount of ethyl 2,;4;d1mtro-.-

6-tert'.-butylpheny1 carbonate; t

10.: A method of protecting plants against infestation by mites and insects, comprising applying to.said plants. an' etfeictive but non-.phytotoxic amount ofn-hexyl 2,4-d1n1tro- 11. A method of protecting plantsiagainst infestation by mites and insects, comprising applying to; said plants an effectivebufhon-phytotoxic amount of methyl 2,4-dinitro- 6- 1 '-methy1buty1) -phenyl carbonate.

.121 .Amethod of protecting plants? against infestation by mites and insects, comprising applying to said'plants an effective but non-phytotoxic' amount of ethyl 2,4.-dinitro- 6- 1'-methylbutyl)-phenyl carbonate. .3

13. A method of protecting. pla'ntsagainst infestation by 'mites and'insects, comprisingapplying to saidplants an effective :but -non-phytotoxi nitro-6-( 1'-methy1buty1)f-pheny1 carbonate.

14. A method of protecting plantsagainst infestation by mites and insects, comprisingapplying to said plants an.

effective but non-phytotoxic amount of 2'-methylbuty1 2,4- dinitr0-6 (-1 '-rnethylbutyl phenyl carbonate.

15. {1A method of protecting plants'against infestation by mites and insects, comprisingapplying to saidplants ant effective but nOn-phYtotOXiQ amount of :3-methylbuty1 2,4- dinitro-.6-( 1 '-r'nethylbutyl) -pheny1 carbonate.

. 16. A method of protecting plants against-infestation by mites and insects, comprisingyapplying to said plants an: eifective but non-phytotoxic amount of'ethyl 2,4-dinitro-= 6-(1'.-methylheptyl) -phenyl carbonate;

17. A method of protecting plants againstinfestation by i mites and insects,- comprising applying to said plants an effective but non-phytotoxic amount' of methyl 2,4-dinitro- 6-(1-methylheptyl)rpheny1 carbonate.

18. :A method ofprotecting plants againstinfestation mites and insects, comprising applying, to.said plants an' eifective but non-phytotoxic. amount of methy1;2,'4-dinitro- 6-( l'-methylhept yl)-phenyl thionothiolocarbonate. 19. A method of protecting plants against infestation by mites and insects, comprising applying to said plants an effective but non-phytotoxici amount of methyl 2, 4-dinitro. 6-'( 1 -rnethylheptyl -phe"ny1 thiolo'carbonate.

References Cited by theEXhminer: 1 "UNITED STATESI PATENTS 3/1964 Sherer et al.;, 167-30 LEWIS GOTTS, Primary Examiner... JULIAN S. LEVITT, Examiner; R. HUFF, Assistant Examiner,

, unt of isopropyl 2,4-di-; 

1. A METHOD OF PROTECTING PLANTS AGAINST INFESTATION BY MITES AND INSECTS, COMPRISING APPLYING TO SAID PLANTS AN EFFECTIVE BUT NON-PHYTOTOXIC AMOUNT OF ISOPROPYL 2,4-DINITRO-6-SEC.-BUTYLPHENYL CARBONATE. 